Triazine derivatives



Patented Aug. 8, 1944 UNITED STATES PATENT OFFICE TRIAZINE DERIVATIVESGaetano F. DAlelio and James W. Underwood, Pittsfield, Mass., assignorsto General Electric Company, a. corporation of New York No Drawing.Application June 19, 1942, Serial No. 447,731

17 Claims. (Cl. 260-249.

This invention relates to new chemical compounds and more particularlyto triazine derivatives. The invention especially is concerned with theproduction of new and useful ketonic-substituted thio triazines.

The chemical compounds of this invention may be represented by thefollowing general formula:

In the above formula 11. represents an integer and is at least 1 and notmore than 2, R represents a member of the class consisting of hydrogenand monovalent hydrocarbon and substituted hydrocarbon radicals, moreparticularly halo-hydrocarbon radicals, and R. represents a member ofthe class consisting of aryl radicals and substituted aryl radicals,more particularly halo-aryl radicals.

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e. g.,

methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl,butenyl, amyl, isoamyl, hexyl, octyl, allyl, methallyl, ethallyl,crotyl, etc.) including cycloaliphatic (e. g., cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g.,phenyl, diphenyl or xenyl, naphthyl, anthracyl, etc.);aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl,propylphenyl, isopropylphenyl, allylphenyl, Z-butenylphenyl, tertiary--butylphenyl, etc.) aryl-substituted aliphatic (e.

g., benzyl, phenylethyl, cinnamyl, phenylpropyl, etc); and theirhomologues, as Well as those groups with one or more of their hydrogenatoms substituted by, for example, a halogen, more parxylyl,-dichlorophenyl, bromotolyl, propenylphen yl, etc. Preferably R inFormula I is hydrogen. However, there also may be' produced inaccordance with the present invention compounds such, for instance, asthose represented by the general formulas:

where n, R and R have the same meanings as given above with reference toFormula I,

The new compounds of this invention may be used, for example, aspharmaceuticals, plasticizers and as intermediates in the preparation ofderivatives thereof such as hydrazo, hydrazine, carbazido,semicarbazido, ureido, amidine, methylol, etc, derivatives of theindividual compound embraced by Formula I. These new compounds areespecially valuable in the preparation of synthetic resinouscompositions. Thus, they may be condensed with, for instance, aldehydes,including polymeric aldehydes, hydroxylaldehydes and aldehyde-additionproducts, to yield condensation products of particular utility in theplastics and coating arts. Such condensation products are more fullydescribed and are specifically claimed in our co-pending applicationSerial'No. 447,730, filed concurrently herewith and assigned to the sameassignee as the present invention. These new compounds also may becompounded with rubber, both natural and synthetic, to modifychlorotolyl, chloro- ,55 the properties of the rubber.

Various methods may be employed to produce the chemical compounds ofthis invention. We prefer to prepare them by effecting reaction, in thepresence of a hydrohalide acceptor, between a mercapto (monomercapto)diamino s-triazine (symmetrical triazine) and a halogenated ketonecorresponding to the formula XCR2n( %-R v where X represents a halogenatom and n, R and R have the same meanings as given above with referenceto Formula I.

Illustrative examples of mercapto diamino [(--NHR)2] s-triazines thatmay be employed, depending upon the particular end-product sought, are:

Mercapto diamino s-triazine (Z-mercapto 4,6-diamino s-triazine;-mercapto 2,6-diamino striazine; G-mercapto 2,4-diamino s-triazine)Z-mercapto 4,6-di-(methy1amin0) s-triazine 2-mercapto 4,6-dianilinos-triazine Z-mercapto 4,6-ditoluido s-triazine z-mercapto 4,6-dixylidinos-triazine 2-mercapto -amino fi-ethylamino s-triazine Z-mercapto4,6-di-(ethylamino) s-triazine 2-mercapto 4,6-di-(propylamino)s-triazine Z-mercapto 4,6-di-(isobutylamino) s-triazine Z-mercapto4,6-di-(propenylamino) s-triazine 2-mercapto 4,6-di-(cyclopentylamino)s-triazine Z-mercapto 4,6-di- (benzylamino) s-triazine Z-mercapto4,6-di-(phenethylamino) s-triazine Z-mercapto 4,6-di-(naphthylamino)s-triazine 2-mercapto 4-allylamino G-butylamino s-triazine Z-mercapto4-isobutylamino 6-cyclopentylamino s-triazine 2-mercapto4-(3-butenylamino) amino s-triazine Z-mercapto 4-pentylamino6-cyclohexylamino striazine 2-mercapto 4-methylamino G-amino s-triazine2-mercapto 4-anilino S-amino s-triazine Z-mercapto 4-fiuoranilinoG-amino s-triazine 2-mercapto l-anilino S-methylamino s-triazine2-mercapto 4-methylamino fi-chloroethylamino s-triazine Z-mercapto4,6-di-(iodoanilino) s-triazine 2-mercapto 4,6-di- (bromopropylamino)s-triazine Z-mercapto 4,6-di-(fluoroanilino) s-triazine 2-mercapto4,6-di-(bromotoluido) s-triazine Z-mercapto 4-hexylamino G-xenylaminos-triazine 2-mercapto 4-cyclohexenylamino S-naphthylamino s-triazineG-isopropyl- Z-mercapto 4-chlorocyclopentylamino G-toluido Z-mercapto4-amino G-naphthylamino s-triazine Z-mercapto 4-isobutylaminofi-neopentylamino s-triazine 2-mercapto l-benzylamino fi-toluidos-triazine Z-mercapto 4-cyclohexylamino 6-xylidino s-triazine 2-mercapto4-phenethylamino 6-chloropropylamino s-triazine Illustrative examples ofhalogenated ketones that may be used, depending upon the desiredend-product, are:

Chloromethyl phenyl ketone Bromoethyl phenyl ketone Iodomethyl phenylketone Chloromethyl tolyl ketones Bromomethyl tolyl ketones Iodomethyltolyl ketones Chloromethyl xylyl ketones Chloromethyl naphthyl ketoneBromomethyl xylyl ketones Bromomethyl naphthyl ketone Chloromethylpropenylphenyl ketones Chloromethyl para-chloroxenyl ketoneAlpha-chloroethyl phenyl ketone Beta-chloroethyl phenyl ketoneAlpha-bromoethyl phenyl ketone Beta-bromoethyl phenyl ketoneAlpha-chloroethyl tolyl ketones Alpha-bromoethyl tolyl ketonesBeta-chloroethyl tolyl ketones Beta-bromoethyl tolyl ketonesChloromethyl chlorophenyl ketones Chloromethyl chlorotolyl ketonesAlpha-chloroethyl chlorophenyl ketones Beta-chloroethyl fluorophenylketones Bromomethyl bromophenyl ketones Alpha-chloroethyl ethylphenylketones Beta-bromoethyl ethylphenyl ketones Alpha-bromoethyl bromophenylketones Alpha-iodoethyl iodophenyl ketones (Alpha-chloro beta-phenylethyl) phenyl ketone (Beta-bromo alpha-ethyl ethyl) tolyl ketones(Alpha-iodophenyl beta-propyl beta-chloro ethyl) phenyl ketone Varioushydrohalide acceptors may be employed. We prefer to use a hydrohalideacceptor that will react with the mercapto triazine to form awater-soluble salt. Examples of such acceptors are the alkali-metalhydroxides, e. g., sodium hydroxide, potassium hydroxide, etc.Additional examples of hydrohalide acceptors that may be used are otherinorganic bases, e. g., calcium hydroxide, barium hydroxide, ammoniumhydroxide, etc.; carbonates of inorganic bases, including the carbonatesof alkali metals; organic amines such as tertiary amines, e. g.,trimethyl amine, triethyl amine, tributyl amine, pyridine, dimethylaniline, quinoline, etc.; quaternary ammonium bases, e. g., tetramethylammonium hydroxide, etc.; and the like.

The reaction between the mercapto diamino s-triazine and the chosenhalogenated ketone may be carried out in any suitable manne, butpreferably is effected in the presence of a suitable solvent or mixtureof solvents. Although various solvents and solvent mixtures may beemployed, for economic reasons and because of their eminent suitabilitywe prefer to use Water or a mixture of water and alcohol. Instead ofalcohol, other solvents may be employed, for instance dioxane. Thereaction may be carried out under a Variety of temperature and pressureconditions, for instance at normal. sub-normal or at eleatmospheric orsuper-atmospheric pressures.

The above reaction may be represented by the following general equation:

In the above equation X represents a halogen atom and n, R and R havethe same meanings as given above with reference to Formula I.

In order that those skilled in the art better may understand how thepresent invention may be carried into eifect, the following examples aregiven by way of illustration. All parts are by weight.

Example I This example illustrates the preparation of (diaminos-triazinyl thio methyl) phenyl ketone, the formula for which is Theabove-stated amounts of thioammeline and sodium hydroxide were dissolvedin the mixture of the stated amounts of alcohol and water, yielding aclear solution. The phenacyl chloride was added to the resultingsolution. The mix was stirred and allowed to react at room temperaturefor 24 hours, followed by heating under reflux at the boilingtemperature of the mass for 1 hour. After cooling, the precipitatecomprising (diamino s-triazinyl thio' methyl) phenyl ketone was filteredofi, washed and dried. A yield of 245 parts of washed and dried productwas obtained. No attempt was made to obtain any more product from themother liquor.

Example 2 Parts Thioammeline 143 Para-chlorophenyl phenacyl bromide 309Sodium hydroxide 40 Water 2,000 AlcohoL 2,000

The same procedure was followed as described under Example 1. Aprecipitate comprising (diamino s-triazinyl thio methyl)para-chloroxenyl ketone was filtered ofi, washed and dried. A yield of350 parts of washed and dried product was obtained. No attempt was madeto obtain any i more produce from the mother liquor.

Example 3 The compound, [4,6-di-(methylamino) s-triazinyl-2 thio methyl]phenyl ketone, is produced in essentially the same manner as describedunder Example 1 with the exception that, instead of thioammeline, anequivalent amount of 2-mercapto 4,6-di-(methylamino) s-triazine isemployed.

Example 4 The compound, [4,6-di-(ethylamino) s-triaziny1-2 thio methyl]para-chloroxenyl ketone, is produced in essentially the same manner asdescribed under Example 2 with the exception that, instead ofthioammeline, an equivalent amount of 2-mercapto 4,6-di-(ethylamino)s-triazine is employed.

Example 5 The compound, [alpha-(diamino s-triazinyl thio) ethyl] phenylketone, is prepared in essentially the same manner as described underExample 1 with the exception that, instead of phenacyl chloride, anequivalent amount of alpha-chloroethyl phenyl ketone is used.

Other examples of the chemical compounds of this invention are listedbelow:

[4,6-di-(methylamino) s-triazinyl-2 thio methyl] tolyl ketones[4,6-di-(ethylamino) s-triazinyl-2 thio methyl] phenyl ketone[4,6-di-(isobutylamino) s-triazinyl-2 thio methyl] phenyl ketone[4,6-di-(propenylamino) s-triazinyl-2 thio methyl] phenyl ketone[4,6-dicyclopentylamino) methyllphenyl ketone (4,6-dianilinos-triazinyl-2 thio methyl) phenyl ketone (4,6-ditoluido s-triazinyl 2thio methyl) phenyl ketone [4,6-di- (naphthylamino) methyl] phenylketone (4,6-diamino s-triazinyl-2 thio methyl) bromotolyl ketones(4,6-diamino s-triazinyl-Z thio methyl) xylyl ketones (4,6-diaminos-triazinyl-2 thio methyl) ethylphenyl ketones (4,6-diamino s-triazinyl2thio methyl) naphthyl ketone (4,6-diamino s-triazinyl-2 thio methyl)propenylphenyl ketones (4,6-dianilino s-triazinyl-Z thio methyl) xenylketone [4,6-di-(methylamino) s-triazinyl-2 thio methyl] propylphenylketones (4,6-dianilino s-triazinyl-2 thio methyl) chlorophenyl ketones[Beta-(diamino s-triazinyl thio) ethyl] phenyl ketone (Diaminos-triazinyl thio methyl) chlorophenyl ketones (Diamino s-triazinyl thiomethyl) bromophenyl ketones (Diamino s-triazinyl thio methyl) iodophenylketones (Diamino s-triazinyl thio methyl) fiuorophenyl ketones[4,6-di-(propylamino) s-triazinyl-Z thio ethyl] phenyl ketones[4,6-di-(fluoroanilino) s-triazinyl-Z thio ethyl] phenyl ketones[Alpha-(diamino s-triazinyl thio) ethyl] tolyl ketones s-triazinyl-2thio s triazinyl 2 thio s-triazinyl-Z thio s-triazinyl-2 thios-triazinyl thio) s-triazinyl-2 thio In a manner similar to thatdescribed above with particular reference to the diamino [(-NHR) 2]ketonic-substituted s-triazines, corresponding derivatives of theasymmetrical and vicinal triazines may be prepared. It also will beunderstood by those skilled in the art from the foregoing description ofthe preparation of a. monothio triazine derivative that similarcompounds may be prepared in which two or three sulfur atoms areattached directly to a carbon atom of the triazine nucleus and whichhave attached to each sulfur atom a -CnR2n-COR' grouping, where n, R andR have the same meanings as given above with reference to Formula I.

The compounds of the present invention are not the equivalent of, andtherefore are not to be confused with, compounds produced by condensingthioammeline in alkaline solution with a halogenated ketonecorresponding to the formula XCH2COCH2R wherein X represents a halogenatom and R represents a member of the group consisting of hydrogen andlower alkyl radicals, more particularly methyl, ethyl, propyl and butylradicals.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. Chemical compounds corresponding to the general formula where nrepresents an integer and is at least 1 and not more than 2, R.represents a member of the class consisting of hydrogen and monovalenthydrocarbon and halo-hydrocarbon radicals, and It represents a member ofthe class consisting of aryl and halo-aryl radicals.

2. Chemical compounds as in claim 1 wherein R represents a hydrogenatom.

3. Chemical compounds as in claim 1 wherein R represents a phenylradical.

4. Chemical compounds as in claim 1 wherein R. represents a hydrogenatom and R represents a phenyl radical.

5. Chemical compounds corresponding to the general formula where nrepresents an integer and is at least 1 and not more than 2, Rrepresents a member of the class consisting of hydrogen and monovalenthydrocarbon and halo-hydrocarbon radicals, and R represents a member ofthe class consisting of aryl and halo-aryl radicals.

6. Chemical compounds corresponding to the general formula NH, t

H I ll HzNC csoi1l-c-1 u where R represents a member of the classconsisting of aryl and halo-aryl radicals.

7. Chemical compounds corresponding to the general formula where nrepresents an integer and is at least 1 and not more than 2, Rrepresents a member of the class consisting of hydrogen and monovalenthydrocarbon and halo-hydrocarbon radicals, and R represents a member ofthe class consisting of aryl and halo-aryl radicals, said methodcomprising effecting reaction, in the presence of a hydrohalideacceptor, between (1) a mercapto triazine corresponding to the generalformula NHR l N RHNG l-SH where R has the meaning above given, and (2) ahalogenated ketone corresponding to the general formula where Xrepresents a halogen atom, and n, R and R have the meanings above given.

15. A method as in claim 14 wherein the hydrohalide acceptor is analkali-metal hydroxide.

16. The method of preparing (diamino s-triazinyl thio methyl) phenylketone which com- CERTIFICATE OF CORRECTION.

Patent No. 2, ,L 2 August 8, 19m.

GAETANO F. DIALELIO, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows Page 1,sec- 0nd column, line #5, for "hydroxylaldehydes" read--hydroxyaldehydes--; page 2,:first column, line 10, last portion of theformula, for "R" read R and second column, line 65, for "manne" 7 read-manner--; and that the said Letters Patent should be read with thiscorrection therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 26th day of September, A. D. 19141;.

Leslie Frazer (Seal) Actingv Commissioner of Patents.

